EP0649828B1 - Verfahren zur Reinigung von 1,1,1,2-Tetrafluorethan - Google Patents

Verfahren zur Reinigung von 1,1,1,2-Tetrafluorethan Download PDF

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Publication number
EP0649828B1
EP0649828B1 EP94402266A EP94402266A EP0649828B1 EP 0649828 B1 EP0649828 B1 EP 0649828B1 EP 94402266 A EP94402266 A EP 94402266A EP 94402266 A EP94402266 A EP 94402266A EP 0649828 B1 EP0649828 B1 EP 0649828B1
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EP
European Patent Office
Prior art keywords
molar ratio
process according
ppm
olefins
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94402266A
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English (en)
French (fr)
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EP0649828A1 (de
Inventor
Bernard Cheminal
André Lantz
Eric Lacroix
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Elf Atochem SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium

Definitions

  • the present invention relates to the field of fluorinated hydrocarbons and more particularly relates to the purification of 1,1,1,2-tetrafluoroethane.
  • F134a This compound, known in the trade under the designation F134a, is in particular intended to replace dichlorodifluoromethane (F12) currently used as refrigerating fluid, but suspected of contributing to the weakening of the stratospheric ozone layer. To do this, F134a must meet quality standards relating to the presence of a priori toxic impurities such as chlorofluorinated olefins.
  • the F134a obtained according to this process or according to other processes generally contains still other olefinic compounds such as butenes or fluorinated propenes.
  • the removed impurity (F1122) is refluorated in F133a, that is to say in a recyclable product.
  • the major drawback of this process lies in the need to have to process a large gas flow rate and therefore to achieve a high reaction volume, which leads to prohibitive investment and maintenance costs.
  • the process also only concerns the elimination of F1122.
  • the present invention provides a particularly effective and economical means for purifying a crude F134a containing unsaturated impurities.
  • the method according to the invention consists in treating in the gas phase, a gaseous mixture of crude F134a, HF and oxygen or air at a temperature between 200 and 350 ° C and under a pressure ranging from atmospheric pressure up to 2.5 MPa, in the presence of a fluorination catalyst, the HF / F134a molar ratio being between 0.05 and 0.5 and the O 2 / F134a molar ratio being between 0.001 and 0.1.
  • the level of olefinic impurities can vary between 50 and 15,000 ppm (0.005 to 1.5%) compared to F134a and is most often between 500 and 5000 ppm (0.05 to 0.5% ).
  • crude F134a may also contain varying amounts of other compounds such as, for example, F133a (0 to 7%), 1,1,1-trifluoroethane (F143a), monochlorotrifluoroethane (F124) and pentafluoroethane (F125); the presence of these saturated impurities in no way detracts from the effectiveness of the process according to the invention.
  • F1122 is generally the most important impurity. Any other olefinic impurities such as F1123, F1243, F1234, F1225, F1318, F1327, F1326 and F1336 are either nonexistent or generally present at lower contents (10 to 500 ppm); among these, the most troublesome are the various F1243, F1234 and F1225.
  • the process according to the invention makes it possible to significantly reduce most of the fluorinated (chloro) olefins. It transforms not only F1122, but also C 3 olefins (F1243, F1234, F1225, ...) which are particularly difficult to remove by treatment with hydrofluoric acid alone.
  • the fluorinated (chloro) olefins such as F1122, 1123, 1243, 1234, 1225, 1318, 1327, 1336, ... can react either with HF or with oxygen.
  • F1122 which is the main impurity can thus transform into F133a or into oxidation products (CO, CO 2 , COF 2 , ).
  • the mechanism of reaction of these olefins with oxygen is not fully known, but it can be assumed that they react by forming an intermediate epoxide which can rearrange:
  • F133a is directly recyclable in the fluorination reactor, it is obviously advantageous to favor the first reaction. Given the differences in reactivity with HF of F1122 and the other olefins present in raw F134a, it has been possible to show that a good choice of operating conditions makes it possible to minimize the underproduction of the oxidation products of F1122 while processing almost quantitatively both F1122 and the other olefins such as F1243, F1234 and F1225.
  • oxygen or air
  • F134a oxygen
  • F133a saturated impurities
  • F133a oxygen
  • these oxidation products are not troublesome and can be easily separated from F134a, it is nevertheless advantageous to minimize these side reactions because they result in a loss of yield.
  • the catalytic treatment in the gas phase of the crude F134a with HF and oxygen or air according to the invention is advantageously carried out at a temperature between 200 and 350 ° C, preferably between 225 and 300 ° C , under a pressure between atmospheric pressure and 2.5 MPa, preferably between atmospheric pressure and 1.5 MPa.
  • the contact time can vary between 10 and 200 seconds, but a contact time of between 20 and 100 seconds is preferred.
  • the HF / F134a molar ratio can vary between 0.05 and 0.5. However, it is preferred to operate with an HF / F134a molar ratio of between 0.125 and 0.200 and, more particularly, a molar ratio close to that corresponding to the azeotrope HF-134a (0.15).
  • the O 2 / F134a molar ratio can vary between 0.001 and 0.1, but it is preferred to operate with an O 2 / F134a molar ratio of between 0.005 and 0.05.
  • the gas stream no longer contains, or only traces of, olefinic impurities and can then be subjected to conventional operations (washing with water, washing with a sodium sulfite solution sodium, drying, distillation ...) to separate HF, unprocessed oxygen or air and saturated compounds other than F134a.
  • the fluorination catalysts to be used for carrying out the process according to the invention can be mass catalysts or supported catalysts, the stable support in the reaction medium being, for example, active carbon, alumina, alumina partially fluorinated, aluminum fluoride or aluminum phosphate.
  • the combustion of the support will be avoided by taking the usual precautions.
  • mass catalysts there may be mentioned more particularly chromium oxide prepared according to any of the methods known to those skilled in the art (sol-gel process, precipitation of hydroxide from chromium salts, reduction of chromic anhydride, etc.).
  • chromium oxide prepared according to any of the methods known to those skilled in the art (sol-gel process, precipitation of hydroxide from chromium salts, reduction of chromic anhydride, etc.).
  • metals such as nickel, iron, manganese, cobalt, zinc, can also be suitable alone or in combination with chromium, in the form of mass catalysts, but also in the form of supported catalysts.
  • the supported catalysts can be used in the form of beads, extrudates, pellets or even, if operating in a fixed bed, in the form of pieces.
  • the form of pellets or beads is generally preferred.
  • This example is intended to illustrate the reactivity of olefins F1243, F1234 and F1225 with HF, without oxygen, in the presence of a fluorination catalyst.
  • the reactor was supplied with a gas mixture consisting of HF and crude F134a in proportions such that the HF / F134a molar ratio is equal to 0.2, that is to say close to the azeotropic composition.
  • the F134a used contained 50 ppm of F1243 + F1234 and 14 ppm of F1225. F1243 and F1234 were not separated under the analysis conditions (gas chromatography) and the 50 ppm correspond to the sum F1243 + F1234. Other analyzes of the same mixture nevertheless showed that the content of F1243 was greater than that of F1234.
  • Rate of olefins leaving the reactor 250 ° C 300 ° C F1243 + F1234 30 20 F1225 12 12
  • F134a contained 2400ppm of F1122. As above, two tests were carried out at 250 ° C and 300 ° C, and in both cases, the residual content of F1122 was less than 5 ppm.
  • the F134a used contained 40 ppm of F1243 + F1234 and 4 ppm of F1225.
  • F134a contained 40 ppm of F1243 + F1234 and 4 ppm of F1225.
  • the F134a used contained inter alia the following impurities:
  • F134a contained 50 ppm of F1243 + F1234 and 14 ppm of F1225.
  • Raw F134a contained among others the following impurities: F124 2% F133a 3.4% F1122 1370 ppm F1243 + F1234 173 ppm F1225 457 ppm
  • the reactor temperature was set at 275 ° C and the feed rate of the mixture was adjusted so as to have a contact time of 80 seconds under a pressure of 1.2 MPa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (9)

  1. Verfahren zur Reinigung von Roh-1,1,1,2-tetrafluorethan (F134a), enthaltend ungesättigte Verunreinigungen, dadurch gekennzeichnet, daß man in der Gasphase eine gasförmige Mischung aus Roh-1,1,1,2-tetrafluorethan, Fluorwasserstoff und Sauerstoff oder Luft bei einer Temperatur zwischen 200 und 350 °C und unter einem Druck, der von Atmosphärendruck bis 2,5 MPa reicht, in Gegenwart eines Fluorierungskatalysators behandelt, wobei das HF/F134a-Molverhältnis zwischen 0,05 und 0,5 liegt und das O2/F134a-Molverhältnis zwischen 0,001 und 0,1 liegt.
  2. Verfahren nach Anspruch 1, bei dem die ungesättigten Verunreinigungen 1-Chlor-2,2-difluorethylen und/oder (chlor)fluorierte C3-C4-Olefine sind.
  3. Verfahren nach Anspruch 1 oder 2, bei dem man unter einem Druck zwischen Atmosphärendruck und 1,5 MPa verfährt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem die Kontaktzeit zwischen 10 und 200 Sekunden, vorzugsweise zwischen 20 und 100 Sekunden, liegt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem das Molverhältnis von HF/F134a zwischen 0,125 und 0,200 liegt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem das Molverhältnis von O2/F134a zwischen 0,005 und 0,05 liegt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem man mit reinem Sauerstoff verfährt.
  8. Verfahren nach einem der Ansprüche 1 bis 6, bei dem man Luft verwendet.
  9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem der Fluorierungskatalysator ein Katalysator in Masse oder ein auf ein Trägermaterial aufgebrachter Katalysator auf Basis von Chrom, Nickel, Eisen, Mangan, Kobalt und/oder Zink ist.
EP94402266A 1993-10-26 1994-10-10 Verfahren zur Reinigung von 1,1,1,2-Tetrafluorethan Expired - Lifetime EP0649828B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9312734A FR2711648B1 (fr) 1993-10-26 1993-10-26 Procédé de purification du 1,1,1,2-tétrafluoroéthane.
FR9312734 1993-10-26

Publications (2)

Publication Number Publication Date
EP0649828A1 EP0649828A1 (de) 1995-04-26
EP0649828B1 true EP0649828B1 (de) 1997-08-27

Family

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Application Number Title Priority Date Filing Date
EP94402266A Expired - Lifetime EP0649828B1 (de) 1993-10-26 1994-10-10 Verfahren zur Reinigung von 1,1,1,2-Tetrafluorethan

Country Status (10)

Country Link
US (1) US5430205A (de)
EP (1) EP0649828B1 (de)
JP (1) JP2543671B2 (de)
KR (1) KR0135362B1 (de)
CN (1) CN1044229C (de)
AU (1) AU659371B1 (de)
CA (1) CA2133613C (de)
DE (1) DE69405189T2 (de)
ES (1) ES2105566T3 (de)
FR (1) FR2711648B1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2694556B1 (fr) * 1992-08-05 1994-09-23 Atochem Elf Sa Procédé de purification du 1,1,1,2-tétrafluoroéthane.
FR2749581B1 (fr) * 1996-06-06 1998-08-14 Atochem Elf Sa Procede de purification d'hydrofluorocarbures satures
US7608574B2 (en) * 2006-08-17 2009-10-27 Honeywell International Inc. Azeotropic or azeotropic-like compositions of 1,1,1-trifuoroethane and 1-chloro-2,2,2-trifluoroethane
JP2010533678A (ja) * 2007-07-20 2010-10-28 ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング 精製ヒドロフルオロアルカンを得るための方法
CN103497087B (zh) * 2013-10-11 2015-03-25 太仓中化环保化工有限公司 一种1,1,1,2-四氟乙烷粗品的脱水方法
JP6176262B2 (ja) * 2015-01-13 2017-08-09 ダイキン工業株式会社 含フッ素オレフィンの製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05972A (ja) * 1991-06-26 1993-01-08 A G Technol Kk 飽和ハロゲン化炭化水素の精製方法
IT1252658B (it) * 1991-12-23 1995-06-20 Ausimont Spa Procedimento per la depurazione dell'1,1,1-trifluoro-2-fluoroetano
FR2698094B1 (fr) * 1992-11-18 1995-01-20 Atochem Elf Sa Purification du 1,1-dichloro-1-fluoroéthane.

Also Published As

Publication number Publication date
AU659371B1 (en) 1995-05-11
JPH07188072A (ja) 1995-07-25
US5430205A (en) 1995-07-04
EP0649828A1 (de) 1995-04-26
DE69405189D1 (de) 1997-10-02
FR2711648B1 (fr) 1996-01-05
CA2133613A1 (fr) 1995-04-27
ES2105566T3 (es) 1997-10-16
KR0135362B1 (ko) 1998-04-23
DE69405189T2 (de) 1998-02-05
FR2711648A1 (fr) 1995-05-05
CA2133613C (fr) 1998-02-03
JP2543671B2 (ja) 1996-10-16
CN1121912A (zh) 1996-05-08
KR950011386A (ko) 1995-05-15
CN1044229C (zh) 1999-07-21

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